CN109232639B - Preparation method of tris (1, 3-dichloropropyl) phosphonate - Google Patents
Preparation method of tris (1, 3-dichloropropyl) phosphonate Download PDFInfo
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- CN109232639B CN109232639B CN201811183153.9A CN201811183153A CN109232639B CN 109232639 B CN109232639 B CN 109232639B CN 201811183153 A CN201811183153 A CN 201811183153A CN 109232639 B CN109232639 B CN 109232639B
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- dichloropropyl
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- 239000007983 Tris buffer Substances 0.000 title claims abstract description 34
- OOKDJDMLPGZAMP-UHFFFAOYSA-N OP(=O)OC(Cl)CCCl Chemical compound OP(=O)OC(Cl)CCCl OOKDJDMLPGZAMP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 26
- 238000004821 distillation Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000012043 crude product Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 9
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 claims 3
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 claims 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 2
- 235000013877 carbamide Nutrition 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 abstract description 18
- -1 1, 3-dichloropropyl Chemical group 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 150000002148 esters Chemical class 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 239000011973 solid acid Substances 0.000 abstract description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 22
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 17
- 239000002244 precipitate Substances 0.000 description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000002791 soaking Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 229910007932 ZrCl4 Inorganic materials 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- 125000005521 carbonamide group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of phosphonic acid tris (1, 3-dichloropropyl) ester, which specifically comprises the following steps of (1) catalyst preparation: the solid acid catalyst is prepared by soluble salts of metals such as Ti, Zr, Fe and the like; (2) preparation of tris (1, 3-dichloropropyl) phosphonate: adding a solid acid catalyst and a reaction material into a reaction kettle at one time, heating to 120-160 ℃, reacting for 6-10 hours, simultaneously evaporating water generated in the reaction in a pressure range of-0.2-0 MPa, and performing alkali washing, water washing and distillation on a crude product to obtain the tris (1, 3-dichloropropyl) phosphonate. The method adopts the self-made catalyst, takes dichloropropanol and phosphorus pentoxide as reaction raw materials to synthesize the tris (1, 3-dichloropropyl) phosphonate, the catalyst is easy to recover and has good catalytic performance, the synthetic process route of the tris (1, 3-dichloropropyl) phosphonate is simple and easy to operate, water is generated by reaction, the process is safe and environment-friendly, and the industrial production is easy to realize.
Description
Technical Field
The invention relates to a preparation method of flame retardant tris (1, 3-dichloropropyl) phosphonate, in particular to a preparation method for synthesizing tris (1, 3-dichloropropyl) phosphonate by catalyzing the reaction of dichloropropanol and phosphorus pentoxide with a solid acid catalyst.
Background
The phosphonic acid tri (1, 3-dichloropropyl) ester contains phosphorus, chlorine and ester group in its molecule, and has relatively great steric hindrance, so that it has the features of less volatilization, high heat stability, stability to water and alkali, and mutual solubility with most organic matters, and is an additive type general flame retardant with the functions of resisting fire, plasticizing, resisting moisture, disturbing static electricity, resisting tensile force and resisting compression, and the halogen atom produced by high temperature decomposition has the function of trapping and burning active free radical to produce high-activity hydroxyl radical or hydrogen to interrupt chain oxidation reaction. And the tris (1, 3-dichloropropyl) phosphonate can be converted into glassy phosphorus pentoxide by thermal decomposition, and a solid coke layer is formed on the surface of the material, so that air and heat are isolated to prevent combustion. On the other hand, the synergistic effect of phosphorus and halogen effectively improves the flame retardant property of the phosphonic acid tris (1, 3-dichloropropyl) ester, phosphorus halide and phosphorus oxide halide generated by thermal decomposition are good radical terminators, the boiling point is high, the specific gravity is high, the residence time in a combustion zone is long, the reaction with radicals is easier, and meanwhile, a covering layer can be formed on the surface of the material to isolate oxygen and heat to prevent combustion. Therefore, tris (1, 3-dichloropropyl) phosphonate is widely used as a good flame retardant and flame retardant plasticizer in unsaturated polyesters, rigid and flexible polyurethane foams, epoxy resins, phenolic resins, flexible polyvinyl chloride and the like.
Currently, tris (1, 3-dichloropropyl) phosphonate flame retardants are generally synthesized by reacting phosphorus oxychloride, phosphorus pentachloride or phosphorus trichloride with an epoxy compound or by reacting amines and aldehydes with phosphorus pentoxide, phosphorus trichloride, phosphorus pentachloride. Regarding the preparation and application of tris (1, 3-dichloropropyl) phosphonate, a large number of foreign literature reports exist, Stauffer chemical company in the United states, Daba chemical company in Japan and the like have been produced for a long time, and in recent years, many scholars in China have studied the synthesis of tris (1, 3-dichloropropyl) phosphonate and realized industrial production.
At present, epichlorohydrin and phosphorus oxychloride are mainly used as raw materials, and TiCl is used4、AlCl3Or Lewis acid is used as a catalyst for synthesis, and related reports are carried out in patent CN 102863468A, CN 107556338A, CN 102807581B and the like. The method adopts a one-step synthesis method, has simple synthesis process, but has obvious defects: firstly, the catalyst has obvious defects, such as instability, easy decomposition in air, difficult separation after reaction, incapability of recycling and reusing the catalyst, environmental pollution and the like. In order to solve the problem of catalyst, the technology is improved by using phosphorus oxychloride and epichlorohydrin as main raw materials, selecting proper solvent and synthesizing phosphonic acid tris (hydroxymethyl) phosphonium chloride under the action of catalyst(1, 3-dichloropropyl) ester, but the process needs reduced pressure distillation to recover the solvent after the reaction is finished, the process is complicated and the reaction time is prolonged.
Secondly, epichlorohydrin is volatile, unstable, has a potential carcinogenic effect, is flammable, the steam and air of the epichlorohydrin easily form an explosive mixture, phosphorus oxychloride has high volatility, high toxicity, serious environmental pollution, easy corrosion of equipment and low reaction conversion rate, the reaction of the epichlorohydrin and the phosphorus oxychloride has high requirement on temperature control, the reaction of the epichlorohydrin and the phosphorus oxychloride has high temperature control, the phenomena of bumping and flushing are easily caused, the epichlorohydrin is easily subjected to self-polymerization or carbonization reaction, the problems of high product chromaticity, high viscosity, turbid appearance and the like are easily caused, and the post-treatment cost is increased. Thirdly, the process is a mode of adding phosphorus oxychloride and a catalyst into a kettle and dripping epichlorohydrin, and the process operation is complex.
In spring red, etc. by using rare earth solid super strong acid SO4 2-/TiO2-Al2O3 /La3+The catalyst is used for catalyzing the reaction of epoxy chloropropane and phosphorus oxychloride to synthesize the tris (1, 3-dichloropropyl) phosphonate, has good stability, is easy to recover and can be repeatedly used, but the defects caused by the reaction of the epoxy chloropropane and the phosphorus oxychloride are not solved, and the catalyst is not beneficial to industrial production.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a safe and environment-friendly preparation method of tris (1, 3-dichloropropyl) phosphonate.
The purpose of the invention is realized by the following contents: a preparation method of tris (1, 3-dichloropropyl) phosphonate comprises the following specific operation steps:
(1) preparation of the catalyst: adjusting the pH value of a system to 9-10 by adding concentrated ammonia water and the like into soluble salt solution of metals such as Ti, Zr, Fe and the like, filtering, washing and drying the obtained metal hydroxide, soaking the metal hydroxide with sulfuric acid or ammonium sulfate with a proper mass percentage concentration of 10-50%, roasting the metal hydroxide for 4-6 hours at 400-700 ℃, and grinding the metal hydroxide to obtain a solid acid catalyst;
(2) preparation of tris (1, 3-dichloropropyl) phosphonate: adding phosphorus pentoxide, dichloropropanol and a self-made solid acid catalyst into a reaction kettle, heating to 120-160 ℃, reacting for 6-10 hours, simultaneously evaporating to remove generated water within the pressure range of-0.2-0 MPa, distilling the excessive dichloropropanol for recycling, and performing alkali washing, water washing and reduced pressure distillation on a crude product to remove water to obtain the tris (1, 3-dichloropropyl) phosphonate.
In the step (1), the soluble salt of the metal is nitrate of Ti, Zr and Fe, wherein the ratio of the amount of each component substance is as follows: 0 to 1.0:0 to 0.5, wherein the amount ratio of each component substance is preferably 0 to 1.0:0 to 0.25
The mass percentage concentration of the sulfuric acid or the ammonium sulfate in the step (1) is 10-50%.
The preparation of the phosphonic acid tris (1, 3-dichloropropyl) ester in the step (2) takes phosphorus pentoxide and dichloropropanol as reaction raw materials, and the reaction chemical equation is as follows:
the feeding mode of the raw materials of phosphorus oxychloride, dichloropropanol and the catalyst for preparing the tris (1, 3-dichloropropyl) phosphonate in the step (2) is a one-time mixed feeding mode.
In the step (2), the feeding molar ratio of the phosphorus pentoxide to the dichloropropanol is 1: 6-18, and preferably, the feeding molar ratio of the phosphorus pentoxide to the dichloropropanol is 1: 8-12.
The amount of the self-made solid acid catalyst in the step (2) accounts for 1-10% by mass of the phosphorus pentoxide feeding amount, and preferably 3-6% by mass.
In the step (2), the reduced pressure distillation is carried out to remove water, the pressure is controlled within-0.06 to-0.09 MPa, and the temperature is controlled within 60 to 80 ℃.
Advantageous effects
(1) Phosphorus pentoxide and dichloropropanol are used as raw materials to replace the traditional epichlorohydrin and phosphorus oxychloride to synthesize the phosphonic acid tris (1, 3-dichloropropyl) ester, water is generated in the reaction process, no hydrogen chloride gas is generated, and the process is safe and environment-friendly;
(2) the reaction materials are added into the kettle in a one-time mode, the process is simple and easy to control, and the cost is low;
(3) the self-made solid acid catalyst catalytic reaction system has good catalytic performance and is easy to recycle and reuse.
Detailed Description
The production method of the present invention will be further described with reference to examples, but the following description is only for the purpose of explaining the present invention and does not limit the contents thereof.
Example 1
(1) Mixing TiCl4Adding concentrated ammonia water into the solution to adjust the pH value of the system to 9-10; filtering, washing and drying the obtained hydroxide precipitate of the metal, and then soaking the precipitate for 2 hours by using sulfuric acid or ammonium sulfate; filtering, drying, calcining at 550 deg.C for 4 hr, grinding to obtain SO4 2-/TiO2A catalyst. (2) Phosphorus pentoxide and dichloropropanol with the mass ratio of 1:8 and SO accounting for 6 percent of the mass fraction of the phosphorus pentoxide4 2-/TiO2The catalyst is added into a reaction kettle at one time, the temperature is raised to 190 ℃ for reaction for 4.0 hours, generated water and excessive dichloropropanol are simultaneously distilled under the pressure range of-0.2-0 MPa, the crude product is subjected to alkali washing, water washing and reduced pressure distillation to remove water to obtain the tris (1, 3-dichloropropyl) phosphonate, and the yield is 85.8%.
Example 2
(1) Reacting ZrCl4Adding carbonamide into the solution to adjust the pH value of the system to 9-10; filtering, washing and drying the obtained metal hydroxide precipitate, and then soaking the precipitate for 2 hours by using sulfuric acid or ammonium sulfate; filtering, drying, calcining at 400 deg.C for 6 hr, grinding to obtain SO4 2-/ZrO2A catalyst. (2) Phosphorus pentoxide and dichloropropanol with the mass ratio of 1:10 and SO accounting for 5 percent of the mass fraction of the phosphorus pentoxide4 2-/ZrO2The catalyst is added into a reaction kettle at one time, the temperature is increased to 180 ℃ for reaction for 5.0 hours, generated water is evaporated at the same time within the pressure range of-0.2-0 MPa, the crude product is subjected to alkali washing, water washing and water removal by reduced pressure distillation to obtain the tris (1, 3-dichloropropyl) phosphonate, and the yield is 85.3%.
Example 3
(1) Reacting ZrCl4、FeCl3Adding concentrated ammonia water into the solution to adjust the pH value of the system to 9-10; filtering, washing and drying the obtained hydroxide precipitate of the metal, and soaking the precipitate for 3 hours by using sulfuric acid or ammonium sulfate; filtering, drying, calcining at 700 deg.C for 6 hr, grinding to obtain SO4 2-/ZrO2-Fe2O3A catalyst. (2) Phosphorus pentoxide and dichloropropanol with the mass ratio of 1:12 and SO accounting for 3 percent of the mass fraction of the phosphorus pentoxide4 2-/ZrO2-Fe2O3The catalyst is added into a reaction kettle at one time, the temperature is increased to 160 ℃, the reaction is carried out for 6.0 hours, meanwhile, the generated water and the excessive dichloropropanol are distilled under the pressure range of-0.2 to 0MPa, the crude product is subjected to alkali washing, water washing and reduced pressure distillation to remove water, so that the tris (1, 3-dichloropropyl) phosphonate is obtained, and the yield is 84.5%.
Example 4
(1) TiCl in a mass ratio of 1:0.254And FeCl3Adding carbonamide into the solution to adjust the pH value of the system to 9-10; filtering, washing and drying the obtained hydroxide precipitate of the metal, and soaking the precipitate for 3 hours by using sulfuric acid or ammonium sulfate; filtering, drying, calcining at 500 deg.C for 5 hr, and grinding to obtain SO4 2-/TiO2-Fe2O3A catalyst. (2) Phosphorus pentoxide and dichloropropanol with the mass ratio of 1:10 and SO accounting for 6 percent of the mass fraction of the phosphorus pentoxide4 2-/TiO2-Fe2O3The catalyst is added into a reaction kettle at one time, the temperature is raised to 160 ℃ for reaction for 8.0 hours, generated water is evaporated at the same time within the pressure range of-0.2-0 MPa, the crude product is subjected to alkali washing, water washing and water removal by reduced pressure distillation to obtain the tris (1, 3-dichloropropyl) phosphonate, and the yield is 86.3%.
Example 5
(1) TiCl in a mass ratio of 1:0.254And ZrCl4Adding concentrated ammonia water into the solution to adjust the pH value of the system to 9-10; filtering, washing and drying the obtained hydroxide precipitate of the metal, and soaking the precipitate for 4 hours by using sulfuric acid or ammonium sulfate; filtering, drying, calcining at 600 deg.C for 5 hr, and grinding to obtain SO4 2-/TiO2-ZrO2A catalyst. (2) Pentaoxidizing the substances in a mass ratio of 1:9Phosphorus dioxide, dichloropropanol and SO accounting for 8 percent of the mass fraction of the phosphorus pentoxide4 2-/TiO2-ZrO2The catalyst is added into a reaction kettle at one time, the temperature is raised to 160 ℃ for reaction for 8.0 hours, generated water is evaporated at the same time within the pressure range of-0.2-0 MPa, the crude product is subjected to alkali washing, water washing and water removal by reduced pressure distillation to obtain the tris (1, 3-dichloropropyl) phosphonate, and the yield is 85.7%.
Example 6
(1) TiCl in a mass ratio of 1:0.25:0.254、ZrCl4、FeCl3、Adding concentrated ammonia water into the solution to adjust the pH value of the system to 9-10; filtering, washing and drying the obtained hydroxide precipitate of the metal, and soaking the precipitate for 4 hours by using sulfuric acid or ammonium sulfate; filtering, drying, calcining at 550 deg.C for 6 hr, grinding to obtain SO4 2-/TiO2-ZrO2-Fe2O3A catalyst. (2) SO accounting for 5 percent of the mass fraction of the phosphorus pentoxide and accounting for 1:8 of the mass ratio of the substances4 2-/TiO2-ZrO2-Fe2O3The catalyst is added into a reaction kettle at one time, the temperature is increased to 160 ℃, the reaction is carried out for 7.0 hours, simultaneously, the generated hydrogen chloride gas is evaporated under the pressure range of-0.2 to 0MPa, the crude product is subjected to alkali washing, water washing and water reduction and distillation to remove water, so that the tris (1, 3-dichloropropyl) phosphonate is obtained, and the yield is 87.8%.
Comparative example
Phosphorus pentoxide and dichloropropanol with the mass ratio of 1:6 and SO accounting for 2 percent of the mass fraction of the phosphorus pentoxide4 2-/TiO2-ZrO2-Fe2O3The catalyst is added into the reaction kettle at one time, the preparation and reaction parameters of other catalysts are the same as those of example 6, and the yield of the phosphonic acid tris (1, 3-dichloropropyl) ester is 75.3%.
The self-made solid acid catalyst can be recycled repeatedly after activation treatment, the feeding molar ratio of phosphorus pentoxide to dichloropropanol is 1:8, the catalyst dosage accounts for 5% of the mass of the phosphorus pentoxide, and the yield of the product ester synthesized by different catalysts for 10 times is as follows:
Claims (4)
1. a preparation method of tris (1, 3-dichloropropyl) phosphonate is characterized by comprising the following specific contents:
(1) preparation of the catalyst: adding concentrated ammonia water or carbamide into soluble salt solution of metals such as Ti, Zr, Fe and the like to adjust the pH value of the system to 9-10; filtering, washing and drying the metal hydroxide obtained by precipitation, and taking sulfuric acid or ammonium sulfate with the mass percentage concentration of 10-50% as SO4 2-Dipping the accelerant for 2-4 hours; filtering, drying, calcining at 400-700 deg.C for 4-6 hr, and grinding to obtain SO4 2-/TiO2、SO4 2-/ZrO2、SO4 2-/Fe2O3Or any combination of two or three thereof;
(2) preparation of tris (1, 3-dichloropropyl) phosphonate: adding phosphorus pentoxide, 1, 3-dichloro-2-propanol and the catalyst prepared in the step (1) into a reaction kettle, heating to 100-160 ℃, reacting for 4-6 hours, simultaneously evaporating generated water within the pressure range of-0.02-0 MPa, and performing alkali washing, water washing and reduced pressure distillation on a crude product to remove water to obtain tris (1, 3-dichloropropyl) phosphonate;
the feeding molar ratio of the phosphorus pentoxide to the 1, 3-dichloro-2-propanol is 1: 8-12;
the dosage of the catalyst accounts for 3-6% of the mass of the phosphorus pentoxide.
2. The preparation method according to claim 1, wherein the soluble salt of the metal in (1) is hydrochloride of Ti, Zr and Fe, and the mass ratio is as follows: 0-1.0: 0-0.5.
3. The preparation method according to claim 1, wherein the raw materials of phosphorus pentoxide, 1, 3-dichloro-2-propanol and the catalyst for preparing the tris (1, 3-dichloropropyl) phosphonate in (2) are in a one-time mixing feeding mode.
4. The preparation method according to claim 1, wherein the reduced pressure distillation and water removal in the step (2) are carried out under the pressure of-0.06 to-0.09 MPa and at the temperature of 60 to 80 ℃.
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